Engineering of Electrochromic Materials as Activatable Probes for Molecular Imaging and Photodynamic Therapy

Electrochromic materials (EMs) are widely used color-switchable materials, but their applications as stimuli-responsive biomaterials to monitor and control biological processes remain unexplored. This study reports the engineering of an organic π-electron structure-based EM (dicationic 1,1,4,4-tetraarylbutadiene, 1²⁺) as a unique hydrogen sulfide (H₂S)-responsive chromophore amenable to build H₂S-activatable fluorescent probes (1²⁺-semiconducting polymer nanoparticles, 1²⁺-SNPs) for in vivo H₂S detection. We demonstrate that EM 1²⁺, with a strong absorption (500-850 nm), efficiently quenches the fluorescence (580, 700, or 830 nm) of different fluorophores within 1²⁺-SNPs, while the selective conversion into colorless diene 2 via H₂S-mediated two-electron reduction significantly recovers fluorescence, allowing for non-invasive imaging of hepatic and tumor H₂S in mice in real time. Strikingly, EM 1²⁺ is further applied to design a near-infrared photosensitizer with tumor-targeting and H₂S-activatable ability for effective photodynamic therapy (PDT) of H₂S-related tumors in mice. This study demonstrates promise for applying EMs to build activatable probes for molecular imaging of H₂S and selective PDT of tumors, which may lead to the development of new EMs capable of detecting and regulating essential biological processes in vivo.